Designation: D 6722 – 01

Standard Test Method for

Total Mercury in Coal and Coal Combustion Residues by
Direct Combustion Analysis1
This standard is issued under the fixed designation D 6722; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

the catalytic section of the furnace, where oxidation is completed and halogens as well as nitrogen and sulfur oxides are
trapped. The remaining decomposition products are carried to
a gold amalgamator that selectively traps mercury. After the
system is flushed with oxygen to remove any remaining
decomposition products, the amalgamator is rapidly heated,
releasing mercury vapor. Flowing oxygen carries the mercury
vapor through absorbance cells positioned in the light path of
single wavelength atomic absorption spectrophotometer. Absorbance peak height or peak area, as a function of mercury
concentration, is measured at 253.7 nm.

1. Scope
1.1 These test methods cover procedures to determine the
total mercury content in a sample of coal or coal combustion
residue.
1.2 The values stated in SI units are regarded as the
standard.
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

NOTE 1—Mercury and mercury salts can be volatized at low temperatures. Precautions against inadvertent mercury loss should be taken when
using this method.

2. Referenced Documents
2.1 ASTM Standards:
D 121 Terminology of Coal and Coke2
D 2013 Method of Preparing Coal Samples for Analyses2
D 3173 Test Method for Moisture in the Analysis Sample of
Coal and Coke2
D 3180 Practice for Calculating Coal and Coke Analyses
from As-Determined to Different Bases2
D 4621 Guide for Accountability and Quality Control in the
Coal Analysis Laboratory2
D 5142 Test Methods for the Proximate Analysis of the
Analysis Sample of Coal and Coke by Instrumental
Procedures2
IEEE/ASTM SI 10 Standard for Use of the International
System of Units (SI): The Modern Metric System3

5. Significance and Use
5.1 The emission of mercury during coal combustion can be
an environmental concern.
5.2 When representative test portions are analyzed according to this procedure, the total mercury is representative of
concentrations in the sample.
6. Apparatus
6.1 There are several configurations of the instrumental
components that can be used satisfactorily for this test method.
Functionally, the instrument shall have the following components: drying compartment, decomposition tube, catalyst tube,
gold amalgamator, amalgamator furnace, measuring cuvettes,
mercury lamp, and detector. The following requirements are
specified for all approved instruments. (Note 2).

3. Terminology
3.1 For definitions of terms used in this standard, refer to
Terminology D 121.

NOTE 2—The approval of an instrument with respect to these functions
is paramount to this test method, since such approval tacitly provides
approval of both the materials and the procedures used with the system to
provide these functions.

4. Summary of Test Method
4.1 Controlled heating of the analysis sample in oxygen is
used to liberate mercury. The sample is heated to dryness in the
instrument and then thermally and chemically decomposed.
The decomposition products are carried by flowing oxygen to

6.1.1 The instrument shall be capable of drying the sample
once it is weighed and introduced.
6.1.2 The instrument shall have a decomposition tube which
shall be operated at a temperature high enough to completely
decompose the sample. The suggested operating temperature is
800°C.
6.1.3 The catalyst in the catalytic tube shall be capable of
completing the oxidation of the sample and trapping halogens
as well as nitrogen and sulfur oxides. The suggested operating

1
This test method is under the jurisdiction of ASTM Committee D05 on Coal
and Coke and is the direct responsibility of Subcommittee D05.29 on Major
Elements in Ash and Trace Elements of Coal.
Current edition approved October 10, 2001. Published December 2001.
2
Annual Book of ASTM Standards, Vol 05.06.
3
Annual Book of ASTM Standards, Vol 14.02.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1

or calibrating agents must be stable with respect to moisture and be pulverized to pass 100 % through a 250 µm (No.3 All CRMs.1. reference coal.D 6722 temperature of the catalytic tube is 550°C.2 Certified Reference Materials (CRMs)—Use Certified Reference Material (CRM) coals with dry-basis mercury values for which confidence limits are issued by a recognized certifying agency such as the National Institute of Standards and Technology (NIST). 6. 6. 11. 6. made of nickel and convenient size suitable for use in the instrument being used.5 The amalgamator shall contain a furnace capable of rapidly heating the amalgamator to release all trapped mercury. reference coals.1 mg.2 Calibration Procedure—Analyze. shall be used. Such CRMS. 7. CAUTION: An indicated problem with linearity of the instrument during calibration can result from contamination of the CRM or calibrating agent as the container becomes depleted. or reference coal.2 Analyze separate test portions for moisture content in accordance with Test Method D 3173 or Test Methods D 5142. 10. 6. with the third falling within the range. Continue analyzing until the results from five consecutive determinations fall within the repeatability interval of these test methods.1.6 The instrument shall have a absorption cell with measuring cuvettes through which the elemental mercury released from the gold amalgamator flows. and for reporting results. 8. Sample 7. These values must have been calculated previously from the certified “dry basis” mercury values and residual moisture determined using either Test Methods D 3173 or D 5142.3. 6. Report 12. two CRM reference coals or calibrating agents that bracket the range of values to be tested. 9. Calibrate the instrument according to the manufacturer’s instructions using these values. reference coals. 6. or calibrating agents must be mixed thoroughly before each use.1. or calibrating agent chosen to represent the level of mercury in the samples to be tested. Procedure 10. 60) sieve. 9. with a sensitivity of 0.65 nm mercury line. or calibrating agent or the calibration procedure must be repeated.1 Oxygen—High purity oxygen. Instrument Preparation 9.1).7 The light source for the atomic absorption process shall be a low pressure mercury lamp.1 Prepare the analysis sample of coal in accordance with Method D 2013 by pulverizing the material to pass a 250-mm (No.2 Analytical Balance. until the absence of drift is indicated. as samples. 6. calibrating agent. Analyze the test portion (see 9. Adjust instrument response. 6.1 All coal CRMs should be in accordance with 8. C = unit mass per detector response established for the analyte during calibration. as samples. Results obtained for the control sample must be within established limits. 8. 9.3. as recommended by the manufacturer.3 Sample Combustion Boats.3 Periodic Calibration Verification and Recalibration—In accordance with Guide D 4621. two of the CRMs or calibrating agents shall bracket the range of mercury to be tested. 8. reference coals. 9. Calculation 11. ~B 3 C! 3 100 D (1) where: A = mg/Kg of the analyte. Reagents 8.1.1 Analyze a test specimen of the analysis sample in accordance with the manufacturer’s instructions. for recording data. The cell shall be heated to avoid any condensation of water or other decomposition products. capable of isolating the 253. 7. analyze a control sample on a periodic basis.4 The instrument shall contain a gold amalgamator fixed to an inert material and shall be capable of trapping all mercury. It is recommended that the user verify the value with the certifying agency before using the CRM coal for quality control purposes. and D = mass of test specimen. as follows: A5 9.3. or all results obtained since the last successful control check must be rejected and the calibration procedure repeated. g. Follow the instrument manufacturer’s recommended procedure to optimize the performance of the instrument. as specified by the instrument manufacturer. or calibrating agents must have precision values of less than or equal to method repeatability.3 Calibration—Select coal CRMs or other calibrating agents and materials specified by the manufacturer that have certified mercury values in the range of samples to be analyzed.1 Report results from the mercury determination on any 2 .2 Adjustment of Response of Measurement System— Weigh an appropriate test portion of certified reference material (CRM). Use the “as-determined” mercury values for calibration. 12.1 Calculate the concentration of mercury. shall be used.1.9 The system may contain a computer for controlling the various operations of the apparatus.1 Assemble the instrumental system in accordance with the manufacturer’s instructions. 9. Records for all calibrations must be in accordance with Guide D 4621. B = detector response for that analyte. on the appropriate sample basis. Analyze. 60) USA Standard Sieve. reference coal. Three such CRMs or calibrating agents are recommended for each range of mercury values to be tested. Repeat this procedure.1. When possible. The results obtained for these samples much be within the stated precision limits of the CRM. portions of a CRM. The calculations can be provided automatically by the instrumental system used for these methods. CRMs. It is therefore recommended that the CRM or calibrating agent be discarded when less than five grams remain in the container.2 and shall be supplied by or have traceability to an internationally recognized certifying organization.8 A narrow bandpass interference filter or monochromator.

Eight labs participated.249750 0.022878 0.020533 0.012604 0. TABLE 2 Comparison of Certified Values for NIST 1630a.053875 0.021821 0.015082 3 . R) has been determined for the following materials as listed in Table A1. designed consistent with Practice E 691.007548 0. of the several common bases that differ solely with respect to moisture.586 x 0. NIST 2692b.039725 0.007 + 0. ppm Repeatability Limit r Reproducibility Limit R 0.022878 0. A comparison of the NIST and SARM values and those obtained in the interlaboratory study are given in Table 2.091250 0.021135 0.015203 0. and SARM 20 were included in the interlabora- NOTE 3—Whenever possible.002358 0.006167 0.114357 0.1 Repeatability (Sr. the test sample uncertainty may be related to those observed when measuring the CRM.008 + 0.088241 0.2 Reproducibility Limit (R)—The value below which the absolute difference between two test results.002930 0.017 – 0.004501 0. carried out in different laboratories using samples taken at random from a single quantity of material that is as homogeneous as possible. r) and Reproducibility (SR.006602 0.005618 0. spanning the concentration range of interest. characterized by repeatability (Sr. is the most meaningful way to investigate measurement bias. Procedures for converting the as-determined concentrations to the other bases are specified in Practice D 3180. carried out on the same sample in the same laboratory by the same operator using the same apparatus on samples taken at random from a single quantity of homogeneous material. may be expected to occur with a probability of approximately 95 %.585786 0.1 Repeatability Limit (r)—The value below which the absolute difference between two test results of separate and consecutive test determinations.0026 –0. R) is described in Table A1.06 – x 0.007377 0.1 The precision of this test method.1 Precision—The precision of this test method for the determination of mercury in coal.017393 0.25 0.033107 0.D 6722 tory study to ascertain possible bias between reference material values and those determined by this method.2 Bias—Certified Reference Materials NIST 1630a.1. Accordingly. PRECISION STATISTICS A1.013788 0.006189 0. ppm CRM Value. 13.007793 0.005386 0.116679 0. was conducted in 2000. may be expected to occur with a probability of approximately 95 %.2 Repeatability Standard Deviation (Sr)—The standard TABLE A1. A1.25 –0.015082 0.031515 0.014187 0. 13.101214 0.020655 0.0093 0 no yes no ANNEX (Mandatory Information) A1. 13.124 0.318536 0. is shown in Table 1.004924 0.012330 0.003669 0.074857 0.13 – Reference CRM Level RR Value. R) Parameters Used for Calculation of Precision Statement Material Average Sr SR r R hvCb Arizona hvAb NIST 2692b hvCb SARM 20 FGD A-1 FGD A-2 HvAb Pennsylvania hvBb Ohio hvBb Colorado sub A Wyoming lig A Texas hvAb NIST 1630a 0.010274 0. r) and reproducibility (SR.1333 0.007333 0. instances could arise where the method of measurement has greater variability than that or those used in certification of the CRM. and SARM 20 with Interlaboratory Study Values for Total Mercury in Coal TABLE 1 Concentration Range and Limits for Repeatability and Reproducibility for Mercury in Coal Hg Concentration Range.3 Reproducibility Standard Deviation (SR)—The standard deviation of test results obtained under reproducibility conditions.124464 0.017331 0.1.042568 0.1. the analysis of several reference materials.008203 0.008171 0.019241 0. 13. A1.017268 0.015730 0.3 An interlaboratory study.008171 0. ppm Bias.0912 0. but a CRM with a related matrix is available.006189 0. When a matrix match is possible the uncertainty in sample measurements can be equated to that observed in measurement of the Certified Reference Material (CRM).004404 0.1 in Annex A1. The details of the study and supporting data are given in ASTM Research Report RR:D-5 1026 filed at ASTM headquarters. The precision characterized by the repeatability (Sr. Precision and Bias 13.005386 0. deviation of test results obtained under repeatability conditions. When such a match is not possible. r) and reproducibility (SR.0938 0. 13. Different methods of measurement of a property may not be capable of equal repeatability. ppm Significant (95% Confidence) NIST 1630a NIST 2692b SARM 20 0. NIST 2692b.017331 0.

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